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WO2012131362A2 - Système étanche à double revêtement comprenant du polyuréthane - Google Patents

Système étanche à double revêtement comprenant du polyuréthane Download PDF

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Publication number
WO2012131362A2
WO2012131362A2 PCT/GB2012/050689 GB2012050689W WO2012131362A2 WO 2012131362 A2 WO2012131362 A2 WO 2012131362A2 GB 2012050689 W GB2012050689 W GB 2012050689W WO 2012131362 A2 WO2012131362 A2 WO 2012131362A2
Authority
WO
WIPO (PCT)
Prior art keywords
coating
barrier
polyurethane
polyurethane resin
coat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2012/050689
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English (en)
Other versions
WO2012131362A3 (fr
Inventor
Sarfaraz Akhtar Khan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun Chemical BV
Original Assignee
Sun Chemical BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sun Chemical BV filed Critical Sun Chemical BV
Priority to KR20137028234A priority Critical patent/KR20140045930A/ko
Priority to CN201280026204.1A priority patent/CN103562248B/zh
Priority to US14/008,431 priority patent/US9902864B2/en
Priority to EP20120719433 priority patent/EP2691432B1/fr
Priority to BR112013024882-3A priority patent/BR112013024882B1/pt
Priority to JP2014501716A priority patent/JP5973547B2/ja
Priority to ES12719433.0T priority patent/ES2536988T3/es
Publication of WO2012131362A2 publication Critical patent/WO2012131362A2/fr
Publication of WO2012131362A3 publication Critical patent/WO2012131362A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing

Definitions

  • the present invention relates to barrier coatings which may be used to coat and impart barrier properties to a variety of materials, notably films used as packaging for foods and pharmaceuticals.
  • the barrier coatings may, for example, be useful in the formation of adhesively formed laminates.
  • the barrier coatings of the invention advantageously have the ability to block the passage of gases including moisture vapour and, as such, may be particularly useful for use in packaging where prevention of ingress of a gas into, or escape of a gas out of, the packaging is desirable.
  • the coatings advantageously provide an effective gas and/or moisture vapour barrier, especially in high relative humidity environments.
  • Synthetic plastics materials have long been used for the packaging of foods and other materials which need protection from handling and from moisture. However, in recent years, it has become appreciated that, in addition, many foods and other sensitive materials benefit from being protected from atmospheric oxygen and other gases. Barrier films and packaging materials, which are intended to reduce, or inhibit the permeation of gases, vapors, aromas and others, have been extensively described. Common barrier compositions include polyesters, PVDC, acrylic polymers, polyamides and others. PVDC coated films are widely used and exhibit excellent barrier properties against oxygen and moisture vapor even at high relative humidity, thereby improving the gas barrier of a range of base films with otherwise poor gas barrier properties.
  • Base films can include biaxially stretched films of polypropylene, nylon, or of polyethylene terephthalate (PET) and cellophane among others. Often these substrates may be laminated with other films and employed for wrapping or packing of a variety of foods to protect against gas egress or ingress. Metalized substrates have also been used for packaging materials due to their excellent gas barrier, however drawbacks are cost, and that they have poor flexibility which causes fracture of the barrier metal layer and are mostly utilized as an intermediate layer of a laminated structures. In the case of PVDC, these packaging materials are disposed of as non-industrial, domestic waste from homes. Unfortunately, when incinerated they give off toxic waste and hazardous gases. Of great concern is the chlorine containing byproducts, which are highly carcinogenic.
  • a barrier coating should provide for example ⁇ 10 cc m 2 /day oxygen transmission (OTR) at 90% RH and 23°C; and ⁇ 10 gm m 2 /day at 90% RH and 38°C moisture vapor transmission (MVTR) (other gases often used to modify the atmospheres inside packages such as carbon dioxide are also important).
  • OTR oxygen transmission
  • MVTR moisture vapor transmission
  • These coatings may be used either as a surface coatings or may be included as part of a multi-layer laminate structure for example for food packaging applications.
  • platy fillers are typically inorganic laminar materials, also referred to as layered inorganic materials, and generally have a high aspect ratio (i.e. the ratio between the length and thickness of a single 'sheet' of material), for example an aspect ratio of greater than about 20 in its exfoliated form, such as between 20 and 10,000.
  • Commonly used inorganic laminar materials have an aspect ratio greater than about 50 for example greater than about 100.
  • Inorganic laminar materials include nanoparticulates, especially nanoparticulate clays.
  • a nanoparticle is a particle having at least one dimension in the nanometre range, i.e. of less than 100 nm.
  • platy meaning high aspect ratio particulates
  • clays increases the barrier effect, usually by creating a more tortuous path for the gas molecules to penetrate the barrier coating.
  • These particles are usually classified as nanoparticles, which are currently attracting much attention particularly with respect to their toxicology and suitability for food packaging components.
  • laminate bond strengths are often reduced.
  • the pre-polymer is then emulsified and reacted with a diamine or other chain-extender to form a water-borne coating composition.
  • the dispersed polyurethane resins of US 2005/0084686 Al and EP 1 674 529 Al have a urethane and urea group concentration of 25 to 60 wt% and an acid value of 5 to 100 mgKOH/g.
  • a one-coat system is prepared using the dispersed polyurethane an exfoliated inorganic filler, such as the synthetic mica ME 100 or montmorilonite and a polyamine compound or silane coupling agent. The one-coat system is reported as providing a high gas barrier either as a surface coat or within a laminate structure.
  • the polyurethane without any ME 100 or montmorilonite is inadequate as a gas or moisture vapor barrier for e.g. food packaging or a suitable replacement for PVDC.
  • the invention provides a barrier layer including the product of combining a polyurethane resin and a multivalent metal cation or other crosslinking agent.
  • the invention provides a barrier layer combining the product of reacting a water-dispersible polyurethane wherein at least 10 wt% of the water dispersible polyurethane is made up of urethane groups, and urea groups if present, and a multivalent metal cation; or combining the product of reacting a solvent-soluble dispersible polyurethane containing acidic functional groups, and a multivalent metal cation.
  • the acid value of the polyurethane is in the range of from 10 to 70 mg KOH/g, especially from about 15 to about 30 mgKOH/g. Acid numbers are typically measured using ASTM D 974.
  • the acid value of the polyurethane used in the invention may be selected from the range in which water dispensability may be imparted to the polyurethane.
  • the resins of the present invention include those described in paragraphs [0024] to [0038] of US 2005/0084686 Al and the solvent soluble prepolymers to example resins PUDl, PUD2, PUD3 and PUD4 described in paragraphs [0066] to [0073] of that document.
  • the acid functionality of the polyurethane is preferably incorporated into the polymer via inclusion of polyhydroxy acid (e.g. carboxylic acid, sulfonic acid, phosphonic acid either singly or in combination in the reaction mixture.
  • polyhydroxy acid e.g. carboxylic acid, sulfonic acid, phosphonic acid either singly or in combination in the reaction mixture.
  • the polyhydroxycarboxylic acid preferably a dihydroxycarboxylic acid
  • dihydroxyC 2 -ioalkane-carboxlyic acids such as dimethylolpropionic acid and dimethylolbutanoic acid
  • dihydroxyCe-ioarene-carboxlyic acids such as 2,6-dihydroxybenzoic acid; and others.
  • These polyhydroxy acids may be used in the form of a salt, typically an ammonium salt, an
  • Coating compositions including the polyurethane resin typically have a viscosity of 10 to 200 mPa.s at 25 °C or 17-60 seconds Zahn cup # 2 at 25 °C.
  • the water based polyurethane dispersions advantageously have an application viscosity of approximately 18 seconds (Zahn Cup 2). This viscosity is suitable for flexo and gravure printing applications. If necessary, the viscosity can be adjusted by changing the concentration of the polyurethane either during the synthesis or post synthesis, and depending on coating application method, the desired application viscosity can be achieved. For example, the viscosity can be adjusted at the dispersion stage, by adjusting the amount of deionized water.
  • the first coating is, for example, a water-based polyurethane dispersion.
  • the water-based polyurethane may, optionally, include further components.
  • the first coating is a solution of a solvent soluble polyurethane in an organic solvent.
  • the polyurethane solution may, optionally, include further components.
  • the first coating may, for example, be a coating composition of the fifth aspect of the invention that comprises a solution of a polyurethane resin, which includes acidic functional groups, in an organic solvent.
  • the barrier coatings of the present application may optionally include additives.
  • additives may include antioxidants, weathering agents, heat stabilizers, thickeners, UV absorbers, oxygen scavengers, oxygen sensors, colorants and the like. These may, for example, be included in amounts of up to 30% with respect to the total weight of the barrier coating. In the case of colorants, the amount used may be higher.
  • Suitable colorants include, but are not limited to organic or inorganic pigments and dyes.
  • the dyes include but are not limited to azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, combinations thereof and the like.
  • the two- coat system of the first aspect of the invention includes a second coating, which includes a crosslinking agent, typically a multivalent metal cation.
  • the superior barrier performance is a synergistic combination of two events, (1) a crosslinking mechanism between multivalent metal cations with the acid groups of the solvent soluble polyurethane and (2) a secondary chelation between multivalent metal ions and the backbone of the urethane groups of the polyurethane.
  • the second coat of the two- coat system is preferably a solution of multivalent metal cations, for example, a solution of zinc cations.
  • the second coating composition is typically a water-based composition and the liquid vehicle is principally water, although organic solvent may also be used as the principal liquid vehicle or be included as a minor component of a predominantly water-based vehicle.
  • those instructions may describe the use of the two-coat system of the first aspect of the invention in the method of the second aspect of the invention and or describe how to prepare the barrier layer of the third aspect of the invention.
  • the polyurethane When preparing a two coat barrier system, it has been found to be advantageous for the polyurethane to react rapidly with metal cations. Rapid reaction facilitates handling of the substance including the barrier coating. Furthermore, rapid reaction is advantageous as the metal cation must react quickly before the liquid vehicle evaporates and/or any additives that maintain the crosslinker in solution or suspension evaporate.
  • volatile additives, such as ammonia to maintain metal cations in solution and/or suspension is advantageous as they are not retained in the barrier layer once formed.
  • no more than 10 wt% of the solid content of the two-coat barrier system, coating composition or barrier layer of the invention is a nanoparticulate material, preferably no more than 5 wt%, more preferably no more than 2 wt%, especially no more than 1 wt% of a nanoparticulate material.
  • Nanoparticulate materials have at least one dimension in the nanometre range, i.e. of less than 100 nm.
  • the two-coat barrier system of the first aspect of the invention and the barrier layer of the third aspect of invention advantageously provides an oxygen transmission rate (OTR) at 90% RH and 23 °C of no more than 8 cm 3 /m 2 /day, preferably no more than 6 cm 3 /m 2 /day, especially no more than 5 cm 3 /m 2 /day, and/or a moisture vapor transmission rate (MVTR) at 90% RH and 38 °C of no more than 15 g/m 2 /day, preferably no more than 12 g/m 2 /day, especially no more than 10 g/m 2 /day wherein the coating weight of the polyurethane resin is no more than 12 g/m 2 , for example, after deposition on a substrate, such as when applied to a 12 ⁇ thick corona surface treated biaxially orientated PET film.
  • OTR oxygen transmission rate
  • MVTR moisture vapor transmission rate
  • the above barrier properties are obtained when the film weight of the polyurethane coating is no more than 10 g/m 2 , preferably no more than 8 g/m 2 , especially no more than about 7 g/m 2 , for example from about 4 to about 6 g/m 2 .
  • the above barrier properties are obtained when the film weight of the metal cation or other crosslinker is no more than 10 g/m 2 , preferably no more than 8 g/m 2 , especially no more than about 7 g/m 2 , for example from about 4 to about 6 g/m 2 .
  • the above reductions in OTR and/or MVTR may, for example, be obtained when using a 12 ⁇ thick corona treated film biaxially orientated PET film, such as, for example Mylar 800 PET film.
  • the OTR and/or MVTR may, for example, be reduced by the above percentages when a 6 g/m 2 coating of crosslinker is applied, for example, applied as an aqueous coating using a #1 K-bar.
  • the OTR of the coated samples can, for example, be determined on a Mocon Oxtran 2/21 gas permeability tester at 23 °C and 90% relative humidity (RH).
  • the MVTR of the coated samples can, for example, be determined on Mocon Permatran-W 3/33 tester at 38 °C and 90% RH.
  • the OTR may, for example, be measured using the ASTM D3985 Standard Test Method for Oxygen Gas Transmission Rate through Plastic Film and Sheeting Using a Coulometric Sensor.
  • the polyurethane does not include triethylamine, which has the potential to be retained, leading to migration issues within the intended package or article.
  • PU 2 A vessel was charged with 2.96 parts of l ,3-bis(isocyanatomethyl)benzene, 8.4 parts of isophorone diisocyanate, 10.4 parts of polyol e.g. bishydroxyethyl terephthalate and 1.82 parts of 2,2-dimethylol propionic acid in 76.34 parts of methylethyl ketone as the solvent.
  • the vessel was purged with nitrogen and stirred at 80 °C for 3 to 10 hours until no unreacted isocyanates remained.
  • a polyurethane resin devoid of any particulates, for example PU1 as prepared as described above, applied as a single coating does not provide sufficient barrier properties at 90% RH.
  • an application of ZnO solution at 6 gsm wet, applied in this example over the top of the polyurethane dispersion coating produces a 29-fold reduction in oxygen transmission rate and 4.7-fold reduction in moisture vapor transmission rate.
  • Table 2 Oxygen transmission and moisture vapor transmission rates of surface coatings prepared from example polyurethane dispersion PU6 and commercial polyurethane dispersions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un système étanche à double revêtement utilisant un revêtement constitué d'une résine de polyuréthane dispersible dans l'eau ou soluble dans un solvant et doté de propriétés innées d'étanchéité aux gaz et à l'humidité, ainsi qu'un revêtement supplémentaire constitué d'un cation métallique multivalent destiné à renforcer les performances d'ensemble en matière d'étanchéité sans qu'il s'avère nécessaire d'ajouter de charges.
PCT/GB2012/050689 2011-03-29 2012-03-28 Système étanche à double revêtement comprenant du polyuréthane Ceased WO2012131362A2 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR20137028234A KR20140045930A (ko) 2011-03-29 2012-03-28 폴리우레탄을 포함하는2-코트 차단시스템
CN201280026204.1A CN103562248B (zh) 2011-03-29 2012-03-28 包含聚氨酯的双涂层阻隔系统
US14/008,431 US9902864B2 (en) 2011-03-29 2012-03-28 Two-coat barrier system comprising polyurethane
EP20120719433 EP2691432B1 (fr) 2011-03-29 2012-03-28 Système étanche à double revêtement comprenant du polyuréthane
BR112013024882-3A BR112013024882B1 (pt) 2011-03-29 2012-03-28 Método de preparação de uma camada de barreira, sistema de barreira de doisrevestimentos, camada de barreira, material de barreira e filme laminado
JP2014501716A JP5973547B2 (ja) 2011-03-29 2012-03-28 ポリウレタンを含む２コートバリア系
ES12719433.0T ES2536988T3 (es) 2011-03-29 2012-03-28 Un sistema de barrera de dos recubrimientos que comprende poliuretano

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BR112013024882B1 (pt) 2020-12-15
US20140212661A1 (en) 2014-07-31
CN103562248B (zh) 2016-10-12
US9902864B2 (en) 2018-02-27
WO2012131362A3 (fr) 2012-12-27
ES2536988T3 (es) 2015-06-01
EP2691432A2 (fr) 2014-02-05
JP5973547B2 (ja) 2016-08-23
KR20140045930A (ko) 2014-04-17
BR112013024882A2 (pt) 2016-12-20
JP2014516764A (ja) 2014-07-17
CN103562248A (zh) 2014-02-05
EP2691432B1 (fr) 2015-01-21

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